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- Author or Editor: L. Katsikas x
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Abstract
Non-isothermal thermogravimetry was performed in a dynamic nitrogen atmosphere, on a series of poly(di-n-propyl itaconates) (PDnPI) and poly(di-iso-propyl itaconates) (PDiPI) which had been prepared in the presence of various amounts of the chain transfer agentn-dodecyl mercaptan (DDM). Differential thermogravimetry (DTG) showed that both polymers degraded in two stages. The DTG curve of PDnPI had a large first peak followed by a smaller shoulder, whereas the DTG curve of PDiPI was composed of two peaks of almost equal heights. The addition of DDM during the polymerisations in both cases resulted in a similar decrease in the relative area of the first peak.
Abstract
The non-oxidative thermal degradation of poly (di-2-chloroethyl itaconate) (PD2CEI) was studied by TG and by analysing the thermal products. The major processes occurring during thermal analysis are crosslinking, depolymerisation and carbonisation. The thermal degradation activation energy increased with increasing sample mass loss. The thermal degradation of PD2CEI was compared to that of the structurally similar poly(2-chloroethyl methacrylate) (P2CMA).
Abstract
Polymethacrylonitrile (PMAN) was prepared by bulk, solution and precipitation polymerization. The thermal stability of the polymer, which is affected by the structure of the chain end groups, was studied by non-isothermal thermogravimetry (TG). On the basis of the differential TG curves of samples prepared by polymerization in the presence of chlorinated solvents, it may be concluded that, in addition to end-chain and random main chain scission initiated depolymerization, hydrogen chloride evolution also occurs during the thermal degradation of PMAN.
Abstract
The thermal stability of poly(methyl methacrylate) (PMMA) photopolymerised using colloidal cadmium sulphide as the photoinitiator was studied by thermogravimetry (TG) and differential TG (DTG). The thermal stability of the CdS initiated PMMA was greater than that of conventional radically polymerised PMMA and approached that of anionically prepared PMMA. The DTG curve of the CdS initiated PMMA was a composite of four peaks, three of which correspond to the three peaks observed in the DTG curve of standard radically prepared PMMA. It is suggested that the additional peak arises from a new mode of depolymerisation initiation, that is, from chain end unsaturation introduced into the polymer chain during polymerisation initiation with the colloidal CdS.
Abstract
TG analysis of lipids is a suitable analytical method that offers the possibility to correlate kinetic parameters of thermal degradation (activation energy) and lipid composition. For this purpose, an inert (nitrogen) or oxidising atmosphere (oxygen) was applied during the thermal treatment (30–220°C) of lipids isolated from intramuscular and fatty tissues (L-IMT and L-FT) of deers and does. Prior to investigation, the extracted samples of lipids were kept at −24°C or +4°C for nine months, thus enabling detection of the influence of storage temperature on the thermal behaviour of the lipids.
Abstract
The effect of molar mass and, in the case of dextran, of the degree of branching on the thermal degradation kinetics of dextran and pullulan was studied in the presence and absence of oxygen. Although the initial mass loss of the dextran samples occurred at higher temperatures than that of the pullulan samples, the overall thermal degradation activation energies were lower for dextran than for pullulan. In the case of dextran the thermal stability was found to decrease with molar mass and degree of branching. The molar mass of pullulan, in the range of 104 to 105 g/mol, appeared to have no significant influence on the thermal characteristics of the samples.
The non-oxidative thermal degradation kinetics of poly(di-n-alkyl itaconates), ranging from the methyl to then-octyl derivatives, were studied by non-isothermal and isothermal TG. The thermal degradation activation energy and characteristic mass loss temperatures were found to decrease with increasing substituent size. The shapes of the DTG curves were dependent on the size of the alkyl substituent. The different DTG maxima were ascribed to various modes of initiation of depolymerisation. The thermal stability of poly(di-n-hexyl itaconate) was found to be independent of the initial molar mass of the sample in the range ofM w from 104 to 107 g/mol.
Abstract
Copolymers of dimethyl itaconate (DMI) and 4-vinylpyridine (4VP) were synthetized in toluene at 60C with0.26 mol% of AIBN as initiator. Their compositions were determined by differential refractometry and by differential scanning calorimetry. The 4VP contents of the copolymer samples ranged between 7 and 75 mol%. The reactivity ratios calculated via the Fineman-Ross method were r 1=0.24 (DMI) and r 2=0.57 (4VP). The thermal degradations of these copolymers were studied. The results of thermogravimetric measurements indicated that the copolymers degrade at lower temperatures than those of their parent homopolymers. A possible explanation of this anomalous behaviour is the formation of thermally unstable structures during the copolymerisation.
Abstract
The application of derivativ thermogravimetry (DTG) to investigate polymerisation mechanisms is illustrated using the radical polymerisation of di-n-alkyl itaconates as well as the photoinitiated polymerisation of methyl methacrylate by colloidal CdS. The thermal properties of the resulting polymers are described. The advantages and disadvantages of DTG are discussed.
